Metallizable polyazo triazine dyestuffs



Patented Oct. 30, 1945 1 METALLIZABLE roLimid rmnzmE Otto Kaiser, Basel, Switzerland, assignor 'to Society of Chemical Industry inBasle, Basel, Switzerland, a Swiss firm No'Drawing. Application May 1, 1944,- Serial No.

' 533,661. In Switzerland June 25, 1943 i 4 Claims. c1. 260153) It :has already been recommended to manu- Iacture dyestuffs containing two different lakeforming elements, that is tosay on the one hand the atom grouping which is formed by coupling diazotized ortho-aminocarboxylic acid in an alkaline medium with 2-amino-5-hydroxynaphtha lene-7-sulfonic acid and, on the other hand, the radicalof a dyestufl' of the kind of the 4-amino- 4'-hydroxy-1:1'-azobenzene-3' carboxylic acid. Swiss Specification No. 137,651, for example, describes the mixed ureas from 1 mol of the amdyestufl from diazotiaed 1-aminobenzene-2-carboxylic acid-4-su1fonic acid and 2-amino-5-hy droxynaphthalene-7-sulfonic acid (coupledin an alkaline medium) and 1 mol. of 4-amino-4-hydroxy-l:1'-azobenzene-3'-carboxylic acid. Swiss Specification No. 137,652 describesa' ternary condensation product from 1 mol of cyanuric chloride, 1 mol each of the two starting azo-dyestuifs of the Just named Swiss Patent No. 137,651 and 1 mol of aniline. Finally, in the French patent of addition No. 37,190 (addition to Patent No. 677,782) there is mentioned the secondary condensation: product from 1 mol. of cyanuricchloride and also 1 mol each of the two starting dyestufi's of Swiss Specification No. 137,651. These dyestuffs are characterized by the propert of yielding copper compounds which are valuable direct dyestuffs. However, when producing the copper compoundsof these dyestuii's on the fiber by after-treating the textile materials dyedwith the metal-free dyestufis with copper, the wetiastness properties oi. the textiles are actually improved, but they are not up to the standard required nowadays.

It has now been found that in contradistinctlon to the above mentioned known dyestuffs, the new products which correspond to thegeneral formula sition to this hydroxyl group, are dyestuffs the copper compounds of which,when produced on the fiber, yield dyeings having excellent fastnss to light and to wet treatment. i .r 2 f The new dyestuffs are made by methodsknown to be suitable for the manufacture of such prod-.

ucts, for example, the methods described below.

They can be obtained by allowing 1 molofja diazotized unsulfonated ortho-aminobenzene care boxylic acid, 1 mol of 2-amino-5-hydroxynaph5 tha1ene-7-sulfonic acid, 1 mol ofcyanuric chloride or 1 mol of cyanuric bromide and 2 molsrof uni sulfonated 4-amino-4 -hydroxy-1 lf-azobenzene 3'-carboxylic acids toreact with one another in such a manner that the diazo compound couples in G-position of the amino-hydroxy-naphthalenesulfonic acid, one halogen atom Of the cyanuric halide reacts with the amino group of the aminohydroxynaphthalene sulfonic acid and one: halo gen atom each of the cyanuric halide reactswith the amino group of one amino-hydroxyazobenej zene carboxylic acid, respectively. 'j

The same products can also be obtained when; in this reaction, one orboth amino-hydroxy-azog benzene carboxylic acids are replaced by amines? of thebenzene series which contain in 4-position to the amino group a second amino group or; a group capable of being converted into an aminb group, and when the reaction is complete, if desired after converting the group capable of being converted into an amino group into such a group, diazotizing or tetrazotizing the condensation product, and then uniting the diazo or tetrazo, compound thusformed with 1 mol or 2 mols (in, the latter case with identical or difierent molecules) ,of a hydroxycompound of the benzene, series which couples with diazo compounds ind,- position to the OH-group. It is obvious that the sequence of the operations can be selected so that the reactions proceed in the desired manner. In this way, reaction of the diazotized condensation products with the aminonaphthoi sulfonic acid residue is avoided. a

For the purpose of introducing the radical R1,

into the new, azo-dyestufisone may start, for cit ample, from the diazo compounds of the follow-,

ing amines: p i y 1 aminobenzene-2-carboxylic acid, l-an'iino-teinobenzene-Z-carboxylic acid, l-amino 4 ben-' zoylaminobenzene-2-carboxylic acid, 1-amin'o-4 bromobenzene-2-carboxylic acid, 1-amino-4 G-di-f bromobenzene-2 carboxylic acid, 1 amino 4- 4-amino4'-hydroxy-1:1'-azobenzene 3 L carboxylic acid, 4-amino-4'-hydroxy-5-methyl-1:Ie

acid, 4-amino-2-methyl-4 -hydroxy-1:1 -azobenhydroxy-1:1'-azobenzene 3 -ecarboxylic :acid, :4- amino-2-chloro-4'-hydroxy-1:1-azobenzene 3- 1'0 azobenzene-3'-carboxylie acid, 4-amino 4'-hy,- V droxy-2-methyl-1:1 -azobenzene 3 --carboxylic.

carboxylic acid, 4-amino-3-methyl-5 -.methoxy- 4'-hydroxy-1 1-azobenzene-'3 -carhoxylic.acid,-l4- amino-2-methyl-5-methoxy-2 methyl 4' hydroxy-1:1'-azobenzene 3'-carboxy1ic acid, 'an'd the like. One or both azodyestufi .radicals can be introduced also in such a manner that one to two halogen atoms .of the cyanuric "halide ..are 'reacjtedlwith compounds such as l-aminolmitrobenzene, '1-amino-f4 acetylaminobenzene, 1- ani'ino-Z-methYL .or '2-methoxyazobenzene, 1 amino-2 methoxy 5-methyl-4 nitrobenzene, and the like. The ni'troor acylamino group isthen converte'diin knownmanner into a primary ami110. group. diazotized andthe diazo compoundis coupled ,with hydroxycarboxylic acid of the benzene series, such as 1-hydroxybenzene-2carbjoxylic acid or l-hydroxy-B- or -6-methylben zene-l2-carboxylic acid.

The new dyestufis are characterized by their afiiriity for cellulose fiber, both for regenerated andalso natural cellulose. They can therefore be. used for dyeing cotton, ramie, jute, viscose rayon, cupra'mmonium silk, staple fibers of regenerated cellulose, if desired,.delustred with titanium oxide, which fibers have been produced according .to Ithe viscose process or according to the cuprammonium process. They can further be .used 'for .dyeing mixtures of these spun mateiiialls with e. g. animal fibers such as wooland silk, Thenew dyestufis dye such materials more orlless yellowish to reddish orange brown shades which become darker "by after-treatment on the fiber withlagentsyel'ding copper, such as, for example, copper sulfate or an alkaline copper-tartrate solution. The dyeings treated in such a manner possessan excellent fastness'to wet treatment combined'with an excellent fastness to light. 1 The following examples illustrate the new process,*without'howeverlimiting it in any way, the parts beingby weight:

' Example :1

, 213,4 parts of '1 -..aminobenzenee2 carboxylic acid areheated to 40 ,C. 'in 200 parts of water, 54 parts of concentrated hydrochloric :acid are .added, cooled with ice to 5 C. and diazotized with 133 partsof sodium nitrite. 'The .clear diazosolution is coupled withl74.4 parts of the .ternary condensation product from 1 mol. of cyanuric chloride orl mol. of cyanuricbromide, 1 mol. .of 2 samino tl-hydroxynaphthalene-7 sulfonic acid, 1 .inofl. of .4-amino-3-methoXy-6- methyl-4 -'h-ydroxy-1.:l-azobenzene-3'-carboxylic acid and .1 mol. of 4-amino-4-hydroxy-1:l-azobenzene-3- carboxylic acid, previously prepared in known manner and dissolved in 2400 parts of water with addition oflZO parts of sodium carbonate. Stirring 'is continuedior some hours and the formed dyestuff is precipitated with common salt. It

corresponds in the free state to theformula:

- When dry it is a. yellow-brown powder which dyes cotton in a feebly alkaline bath weak brownish orange shades. When adding a copper salt solution firom-copp'er sulfate and sodium tartrate 'to the'dyebath, the color tint changes to orange- ,brow-n theldyeing being fast to washing and light.

:When usingzin the triazine product instead of the ,4 amino-3-methoxy-5-methyl-4'-hydroxy- 1: l-azobenzene-3'-carboxylic acid the 4-amino- 00 OH .OH

and dyes cottonsimilar shades having the same fastness vproperties. V v

Products .obtainableaccording to the .first paragraph of this example can also be prepared by coupling at first the .diazotized 1-aminobenzene Z-carboxylic acid with =2-.amino-.5-hy.droxynaphthalene- 7-.sulfonic .acid in an alkaline medium and then. reacting in any-desiredsequence 1 'mol. of the resultingfmonoaminoazo-dyestuif,. 1 molnof 4 -ramino 3 -.=methoxy -:6 -methyl-4--h-ydroxy- 1:1"-azobenzene13ecarboxylic-acid-and 1 :mol. of 4-amino-4' hydroxy-l: l --azobenzenecarboxylicacid .with 1 mol. ofcyanuric chloride.

The product obtainable according to thesecond paragraph of .this example can also be prepared by producing at first .a ternary condensation ,pliQdllCt .from v1 mol. of the =azo-dyestufi from .diazotized .l-aminobenzene-.2----carboxylic acid and. 2eaminoe5-hydroxynaphthalene-7 sulfonic acid and 2.mols. of 1-,amino-4-acetylaminobenzene, then splitting ofi the .-two..acetyl- -groups by treating with saponifying agents; tetrazotizing the resulting diamino compoundand .finally-cowpling ,with 2 .mO1S. .Of -1-:hydroxylcenzene -.2 carbo-xylicacid.

l The procedure .is similar with 'the =diiferentcintermediate products indicated in the introduc: tion, dyestuffs being thus obtained which behave similarly to the products of the first two paragraphs of thisexample.

Example 2 1 mol. of diazotized 1-aminobenzene-2-carboxylic acid is coupled in an alkaline medium in known manner withimol. of Z-aminQ-Erh'ydroX- ynaphthalene-7-sulfonic acid. 38.7:parts'aof :the resulting .monoazo-dyestufl are a dissolved :in :1500 partsof water assodium salt and graduallyzadded, while vigorously stirring, to 18.4 parts of cyanuric chloridesuspended in 500 parts .of water. The hydrochloric acid thusformed is neutralized with the corresponding quantity of sodium 'carbonate. When .th e condensation is-complete, .51 Aparts of 4-amino-4'-hydroxy-1:1' azobenzene 3' carboxylic acid dissolved as sodium salt in 1000 parts of water are added and the temperature of the mixture is raised to 40 C. This temperature is maintained for 2 hours, the resulting hydrochloric acid is again neutralized with the corresponding quantity of sodium carbonate and the temperature raised to 80-85 C. This temperature is maintained for 3 hours and the formed dyestufl. is separated as sodium salt by means of common salt. When dry it is a yellow-brown powder. The new dyestufl corresponds to the product of the second paragraph of Example 1.

Example 3 100 parts of cotton are introduced at 40-50 into a dye-bath consisting of 3000 parts of water, 1.5 parts of the dyestufi, prepared according to the first paragraph of Example 1, and 2 parts of anhydrous sodium carbonate. The bath is heated to 90-95 0. within A hour, 30 parts of crystallized sodium sulfate are added and dyeing is continued for hour at this temperature, A solution neutralized with caustic soda solution consisting of 2 parts of crystallized copper sulfate and 2.5 parts of tartaric acid in 100 parts of water is added to the dye-bath and the cotton is treated for V2 hour at about 95 C. It is then rinsed and dried as usual. The cotton is dyed fast orange brown shades.

As mentioned already in the introduction, the dyestuffs of the present invention can also be used for dyeing mixed fabrics, for example mixtures of wool and viscose cellulose wool. In such cases it is appropriate to dye in a neutral bath in the presence of sodium chromate or potassium chromate.

What I claim is: 1. The dyestufis corresponding in the free form wherein Rl, R2, R3 and R4 represent unsulfonated benzene nuclei, R1 and R3 containing the NH- group and the azo-group linked in 1:4-position to one another, and R2 and R4 containing a hydroxyl group in 4-position to the azo-group and a carboxyl group in ortho-position to this hydroxyl group.

3. The dyestuif corresponding in the free form to the formula COOH 000K in N=N II/ N OCH;

N-o c-N OH HOaS H H CH3 4. The dyestuff corresponding in the free form to the formula 

